Interest grew in the development of new oxidising agents as a
replacement for high purity meta-chloroperbenzoic acid (mCPBA) and
avoiding the difficulty in obtaining high strength hydrogen peroxide.
Magnesium monoperoxyphthalate (MMPP) has been advertised as a
replacement. However due to problems of solubility of this oxidant in a
number of solvents, it cannot be considered as a complete substitute for
mCPBA.
An oxidising agent is required to either complement MMPP, or succeed
mCPBA entirely.
This thesis describes the investigation of some hydrogen peroxide
adducts as a possible contender to the extremely versatile oxidant, mCPBA.
Urea-hydrogen peroxide adduct (UHP) in combination with either
trifluoroacetic or acetic anhydride was used for the in situ formation of
percarboxylic acids. Oxidations of various functional groups were carried
out using these peracids. Reactions include: the epoxidation of terminal,
electron deficient alkenes, such as octene, by trifluoroperacetic acid; the
epoxidation of electron rich alkenes, such as styrenes and cyclohexenes, by
peracetic acid; Baeyer-Villiger reactions of both aliphatic and alkyl aryl
ketones by trifluoroperacetic acid; the conversion of anilines into
nitrobenzenes; the oxidation of tertiary amines and sulphides; and the
oxidative cleavage of dimethylhydrazones.
A number of other hydrogen peroxide adducts were produced and their
performance in various oxidation reactions was compared to that of ureahydrogen
peroxide.
Experiments in the formation of adducts to induce chirality in
epoxidation reactions were also undertaken.

Description:

A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy of Loughborough University.